EP0204038B1 - Verfahren zum Betrieb einer Sekundärbatterie - Google Patents

Verfahren zum Betrieb einer Sekundärbatterie Download PDF

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Publication number
EP0204038B1
EP0204038B1 EP85303944A EP85303944A EP0204038B1 EP 0204038 B1 EP0204038 B1 EP 0204038B1 EP 85303944 A EP85303944 A EP 85303944A EP 85303944 A EP85303944 A EP 85303944A EP 0204038 B1 EP0204038 B1 EP 0204038B1
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EP
European Patent Office
Prior art keywords
battery
secondary battery
voltage
power
converter
Prior art date
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Expired - Lifetime
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EP85303944A
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English (en)
French (fr)
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EP0204038A1 (de
Inventor
Takafumi Hashimoto
Yoshihide Kamanaka
Tadashi Ashikaga
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Meidensha Corp
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Meidensha Corp
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Publication date
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Priority to DE8585303944T priority Critical patent/DE3583863D1/de
Priority to AT85303944T priority patent/ATE66546T1/de
Publication of EP0204038A1 publication Critical patent/EP0204038A1/de
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Publication of EP0204038B1 publication Critical patent/EP0204038B1/de
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
    • H01M10/44—Methods for charging or discharging
    • H—ELECTRICITY
    • H02—GENERATION; CONVERSION OR DISTRIBUTION OF ELECTRIC POWER
    • H02J—CIRCUIT ARRANGEMENTS OR SYSTEMS FOR SUPPLYING OR DISTRIBUTING ELECTRIC POWER; SYSTEMS FOR STORING ELECTRIC ENERGY
    • H02J7/00—Circuit arrangements for charging or depolarising batteries or for supplying loads from batteries
    • H02J7/007—Regulation of charging or discharging current or voltage
    • H02J7/0071—Regulation of charging or discharging current or voltage with a programmable schedule
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Definitions

  • the present invention relates to a method of operating a secondary battery to recondition it, involving repeated charge and discharge cycles, in which zinc (Zn) is used as the negative electrode active material.
  • Examples of secondary batteries using zinc (Zn) as the negative electrode active material include a zinc-bromine, zinc-chlorine, nickel-zinc, air-zinc battery etc.
  • the operation of this type of secondary battery is effected by a complete discharge method which is intended to completely dissolve the zinc on the negative electrode for the purpose of increasing the charge and discharge battery life. With this complete discharge operation, the secondary battery is discharged until the battery voltage and the load current are substantially reduced to zero.
  • Patent Abstracts of Japan, Vol. 6, No. 243 (E-145)(1121) 02.12.1982 relating to JP-A-57143273 discloses a capacity restoring method for a lead-acid battery.
  • the polarity of the terminal voltage is reversed through compulsory discharge when the capacity of the battery is extremely low. Following the discharge compulsory charge is carried out at a constant current.
  • GB-A-1599076 discloses, as a background to apparatus for recharging dry electric power cells, a negative discharging current which is applied to a dry cell to polish the zinc electrode to improve the surface layer in between recharges. This is used to improve the recharging.
  • a method of operating a secondary battery (10) to recondition the battery in which the secondary battery includes at least one unit cell using zinc as an active material for the negative electrode (10M) in an electrolyte and which is adapted to be charged and discharged repeatedly, the method comprising the steps of : discharging the secondary battery until the voltage of the battery has been reduced to a predetermined positive value; and then electrically and switchably connecting the positive electrode (10P) of the battery to the negative output terminal (20M) of direct current supply means (20) and connecting the negative electrode of the battery to the positive output terminal (20P) of the direct current supply means; flowing a reversed charging current from the negative electrode to the positive electrode through the electrolyte of the battery from the direct current supply means until the battery voltage has been further reduced below the zero value and has reached a predetermined negative value to cause the zinc on the negative electrode to be completely dissolved into the electrolyte; electrically and switchably connecting the positive electrode (10P) of the battery to the positive output terminal (20P) of the direct current supply
  • the energy generated from the secondary battery is preferably regenerated by means which is capable of converting the d.c power to a stepped-up a.c. power.
  • Fig. 1 shows a circuit for effecting the complete discharge of a cell stack secondary battery 10.
  • the secondary battery 10 is connected to a charging and discharging circuit which is not shown.
  • the charging and discharging circuit includes a load which is supplied with the power from the secondary battery 10.
  • the secondary battery 10 is shown connected to a series circuit of a switch 12 and a resistor 14.
  • FIG. 2 there are illustrated respectively in the characteristics (A) and (B) variations in the voltage and current of the secondary battery 10 when its charge, discharge and said complete discharge are effected.
  • Shown at (C) are the modes of operation of the secondary battery 10.
  • the secondary battery 10 is charged from a time t1 to a time t2 by the charging and discharging circuit which is not shown.
  • the charging and discharging circuit is opened.
  • the power is supplied to the load from the secondary battery 10 through the charging and discharging circuit and the secondary battery 10 is discharged.
  • the charging and discharging circuit is again opened.
  • the complete discharge of the secondary battery 10 is effected.
  • the switch 12 shown in Fig. 1 is turned on first at the time t5. This operation connects the positive and negative electrodes of the secondary battery 10 to the resistor 14 and the complete discharge of the secondary battery 10 is started.
  • the battery voltage gradually decreases as shown in (A) in Fig. 2, and also the battery current decreases gradually as shown in (B).
  • the battery voltage and current of the secondary battery 10 become substantially equal to zero at the time t6.
  • the complete discharge operation is completed and the charge of the next cycle is started.
  • the zinc deposits on the negative electrode during the charge, and upon the discharge the zinc on the negative electrode is dissolved into the electrolyte.
  • the complete discharge is effected, the whole zinc on the negative electrode must be dissolved into the electrolyte.
  • some of the zinc on the negative electrode is not dissolved completely into the electrolyte. Therefore, when the charge of the next cycle is effected, the zinc is further electrodeposited on the remaining zinc on the negative electrode. If this electrodeposition of the zinc develops into an abnormal electrodeposition in the form of dendrite, then the battery is finally short-circuited.
  • Fig. 3 shows an exemplary circuit for performing an operating method according to a first embodiment of the invention.
  • a cell stack secondary battery 10 which in this case uses zinc as the negative active material, has a positive electrode 10P connected to a contact 16A of a switch 16.
  • a negative electrode 10M of the secondary battery 10 and the other contact 16B of the switch 16 are connected to a polarity reversing switch 18.
  • the polarity reversing switch 18 includes fixed contacts 18A, 18C, 18D and 18F, and ganged movable contacts 18B, 18E.
  • the fixed contacts 18A and 18F are interconnected and the fixed contacts 18C and 18D are interconnected.
  • the contact 16B of the switch 16 is connected to each of the fixed contacts 18C and 18D of the polarity reversing switch 18.
  • the negative electrode 10M of the secondary battery 10 is connected to each of the fixed contacts 18A and 18F of the polarity reversing switch 18.
  • the contact 18B of the polarity reversing switch 18 is connected to a negative terminal 20M of a d.c. power source 20. Also, the contact 18E of the polarity reversing switch 18 is connected to a positive terminal 20P of the d.c. power source 20. In the polarity reversing switch 18, the contact 18B can be engaged with either of the contacts 18A and 18C. Also, the contact 18E can be engaged with either of the contacts 18D and 18F. The interengagements of these contacts are made in an interlocked manner. When the contact 18B is engaged with the contact 18A, the contact 18E is engaged with the contact 18D; thus, the positive electrode 10P of the secondary battery 10 is connected to the positive terminal 20P of the d.c.
  • the negative electrode 10M of the secondary battery 10 is connected to the negative terminal 20M of the d.c. power source 20.
  • the contact 18B of the polarity reversing switch 18 is engaged with the contact 18C, the contact 18E is engaged with the contact 18F; thus, the positive electrode 10P of the secondary battery 10 is connected to the negative terminal 20M of the d.c. power source 20 and the negative electrode 10M of the secondary battery 10 is connected to the positive terminal 20P of the d.c. power source 20.
  • the polarity reversing switch 18 can also be set into an open position in which its movable contacts 18B and 18E are out of engagement with all of the fixed contacts 18A, 18C, 18D and 18F.
  • the secondary battery 10 is also connected to a charging and discharging circuit which is not shown.
  • the charging and discharging circuit includes a load which is supplied with the power from the secondary battery 10.
  • Fig. 4(A) shows variations in the battery voltage of the secondary battery 10 when the operating method of the embodiment is performed. Shown in (B) are variations in the battery current of the secondary battery 10 in the similar case. Also, shown in (C) are the modes of operation in the similar case.
  • the charge of the secondary battery 10 is effected first during the interval from t10 to t11 in Fig. 4. This charge is effected with a constant voltage e s and constant current by the charging and discharging circuit which is not shown. Note that the polarity reversing switch 18 shown in Fig. 3 is open. During the interval from t11 to t12, the charging and discharging circuit is opened. In this period, the battery voltage e v of the secondary battery 10 is lower slightly than the charging voltage value e s .
  • the secondary battery 10 is discharged by the charging and discharging circuit which is not shown.
  • the discharge current flows constantly throughout the period, and the discharge voltage remains essentially constant until the final stage of the period and then decreases gradually by a small amount, and the power is supplied to the load.
  • This discharge voltage is lower than the open battery voltage e v of the secondary battery 10. Note that the direction of the battery current I L flowing during the discharge is opposite to the current flowing during the charge.
  • the discharge is terminated and the charging and discharging circuit is again opened.
  • the open battery voltage e v of the secondary battery 10 recovers gradually to a voltage level corresponding to the open battery voltage value at the open circuit period from t11 to t12 after the charging operation.
  • the reversed charge of the secondary battery 10 is effected.
  • the polarity reversing switch 18 is operated to engage contact 18B with contact 18C, and to engage contact 18E with contact 18F.
  • the switch 16 is turned on.
  • the positive electrode 10P of the secondary battery 10 is connected to the negative terminal 20M of the d.c. power source 20 and the negative electrode 10M of the secondary battery 10 is connected to the positive terminal 20P of the d.c. power source 20; thus, the reversed charge of the secondary battery 10 is effected.
  • the battery voltage e v of the secondary battery 10 decreases gradually and it is eventually reversed in polarity.
  • the battery current I L of the secondary battery 10 flows constantly in the same direction as in the case of the discharge during the interval from t12 to t13.
  • the battery voltage e v of the secondary battery 10 becomes a predetermined negative voltage -e1 as shown in Fig. 4(A).
  • the polarity reversing switch 18 is operated so as to reverse the polarity of the d.c. power source 20 connected to the secondary battery 10.
  • the contact 18B of the polarity reversing switch 18 engages the contact 18A and the contact 18E and engages the contact 18D.
  • the positive electrode 10P of the secondary battery 10 is connected to the positive terminal 20P of the d.c. power source 20 and the negative electrode 10M of the secondary battery 10 is connected to the negative terminal 20M of the d.c. power source 20.
  • the reversed discharge of the secondary battery 10 is effected starting at the time t15.
  • the battery voltage e v of the secondary battery 10 is gradually increased from the negative voltage -e1 to approach zero and then it is eventually reversed and restored to the original polarity.
  • the battery current I L of the secondary battery 10 flows constantly in the same direction as in the case of the charging during the interval from t10 to t11.
  • the battery voltage e v of the secondary battery 10 reaches the initial voltage e s at the end of the charging at the time t11 as shown in Fig. 4(A).
  • the switch 16 is turned off and then the open battery voltage decreases slightly.
  • the open circuit of the secondary battery 10 by this operation is continued up to a time t17, and the essential normal charge is then effected by the charging and discharging circuit which is not shown.
  • the reversed charge of the secondary battery 10 is effected after the termination of its normal discharge.
  • This reversed charge reverses the polarities of the electrodes 10P and 10M of the secondary battery 10.
  • the zinc remaining on each negative electrode of the cell stack secondary battery 10 upon the termination of the normal discharge at the time t13 is completely dissolved into the electrolyte by the reversed charge.
  • the reversed discharge is effected and the secondary battery 10 is restored to the normal polarity and state.
  • the open-circuit mode (t16 to t17) exists between the reversed discharge mode and the normal charge mode as shown in Fig. 4(C).
  • this open-circuit mode is not especially required at all time. Therefore, it is possible to arrange so that the normal charge of the secondary battery 10 is started at the time t16.
  • the electrolyte circulating pumps may be stopped during the operation in the reversed charge mode and the reversed discharge mode, respectively. If the electrolyte circulating pumps are stopped, the electrolytes in all the unit cells of the secondary battery 10 are made stationary.
  • the electrolyte circulating pumps which are not shown are stopped at the time t14 in Fig. 4 and the operation of the pumps is restarted at the time t17.
  • the reversed charge and discharge operations are performed for every normal charge and discharge cycle of the secondary battery 10 or at intervals of several cycles.
  • Fig. 5 shows an exemplary circuit for performing an operating method according to the second embodiment of the invention.
  • a secondary battery 10 is connected to an a.c.-d.c. converter circuit 22 including a step-up and step-down circuit (hereinafter simply referred to as a.c.-d.c. converter circuit).
  • the a.c.-d.c. converter circuit 22 is also connected to a series circuit of a switch 24 and an a.c. power source 26.
  • a.c.-d.c. converter circuit 22 Connected to the a.c.-d.c. converter circuit 22 are a battery voltage detecting circuit 28, a battery current detecting circuit 30 and a control circuit 32.
  • the control circuit 32 controls the operation of the a.c.-d.c. converter circuit 22 in accordance with the detection signals from the battery voltage detecting circuit 28 and the battery current detecting circuit 30.
  • Figs. 6(A) to (C) show the battery voltage e v and the battery current I L of the secondary battery 10 during its operation and the modes of operation as in the case of Fig. 4.
  • the switch 24 is turned on and the charge of the secondary battery 10 is effected.
  • the a.c. power from the a.c. power source is converted to a d.c. power by the a.c.-d.c. converter circuit 22.
  • the charge of the secondary battery 10 is effected by this d.c. power.
  • the charging voltage and the charging current during the charge are respectively detected by the battery voltage detecting circuit 28 and the battery current detecting circuit 30.
  • the control circuit 32 controls the a.c.-d.c. converter circuit 22. This control maintains the charging voltage and the charging current at the desired values as shown in Figs. 6(A) and (B), respectively.
  • the switch 24 is again turned on and the secondary battery 10 is discharged.
  • the d.c. power from the secondary battery 10 is stepped-up and converted to an a.c. power by the a.c-d.c. converter circuit 22.
  • the d.c. power is converted to an a.c. power and then stepped-up.
  • stepped-up a.c. power is returned to the a.c. power source 26 or regenerated.
  • the current flowing to the a.c. power source 26 during the discharge is detected by the battery current detecting circuit 30.
  • the control circuit 32 controls the a.c.-d.c. converter circuit 22. As a result of this control, the current flowing to the a.c. power source 26 is controlled at the desired value.
  • the reversed charge of the secondary battery 10 is effected.
  • the battery a.c.-d.c. converter circuit 22 is connected to the secondary battery 10 in opposite polarity relation with each other.
  • the secondary battery 10 and the a.c.-d.c. converter circuit 22 are connected opposite in polarity to the connections during the charge in the interval from t20 to t21.
  • the battery voltage e v of the secondary battery 10 is decreased gradually and eventually its polarity is reversed.
  • the battery current I L of the secondary battery 10 flows constantly in the same direction as in the case of the discharge during the interval from t22 to t23.
  • the control circuit 32 controls the a.c.-d.c. converter circuit 22 in the following manner. Firstly, the a.c.-d.c. converter circuit 22 is controlled in such a manner that the d.c. power from the secondary battery 10 is converted to a stepped-up a.c. power until the battery voltage e v is reduced to zero (the interval from t24 to t25). By virtue of this control the energy from the secondary battery 10 is regenerated or returned to the a.c. power source 26. Then, the a.c.-d.c.
  • converter circuit 22 is controlled in such a manner that the a.c. power from the a.c. power source is converted to a d.c. power until the battery voltage e v reaches a predetermined negative voltage -e2 (the interval from t25 to t26).
  • a predetermined negative voltage -e2 the interval from t25 to t26.
  • the reversed discharge of the secondary battery 10 is effected.
  • the terminal connections between the a.c.-d.c. converter circuit 22 and the secondary battery 10 are interchanged.
  • the secondary battery 10 and the a.c.-d.c. converter circuit 22 are connected in the same polarity relation as in the case of the charge during the interval from t20 to t21.
  • the battery voltage e v of the secondary battery 10 is gradually increased from the negative voltage -e2 toward zero and it is eventually reversed to restore the original polarity.
  • the battery current I L flows constantly in the same direction as in the case of the charge during the interval from t20 to t21.
  • the battery voltage e v of the secondary battery 10 is detected by the battery detecting circuit 28 and its detection signal is supplied to the control circuit 32.
  • the control circuit 32 controls the a.c.-d.c. converter circuit 22 in the following manner. Firstly, the a.c.-d.c. converter circuit 22 is controlled in such a manner that the d.c. power from the secondary battery 10 is converted to a stepped-up a.c. power until the battery voltage e v is increased from the negative voltage -e2 to zero (the interval from t26 to t27).
  • the energy from the secondary battery 10 is returned to the a.c. power source 26.
  • the ac.-d.c. converter circuit 22 is controlled in such a manner that the a.c. power from the a.c. power source 26 is converted to a d.c. power until the battery voltage e v is increased from zero to reach a normal-polarity present voltage e T (the interval from t27 to t28).
  • the normal charge of the secondary battery 10 is effected by the energy from the a.c. power source 26.
  • the battery voltage e v of the secondary battery 10 is restored to the original voltage e T as shown in Fig. 6(A).
  • the switch 24 is turned off.
  • the open-circuit condition of the secondary battery 10 by this operation is continued up to a time t29.
  • the switch 24 is again turned on and the essential normal charge is effected.
  • Fig. 7 shows a detailed example of the embodiment shown in Fig. 5.
  • the a.c.-d.c. converter circuit 22 includes first and second converters 22A and 22B, a step-up circuit 22c and a d.c. reactor 22D.
  • each of the converters 22A and 22B comprises switching elements such as thyristors or transistors arranged in a three-phase bridge connection. This connection is generally referred to as a thyristor Ward-Leonard type.
  • the first and second converters 22A and 22B are connected so that they are opposite in polarity to each other, that is, they are arranged in an inverse parallel connection.
  • the converters 22A and 22B are connected to the a.c. power source 26.
  • the a.c. power source 26 comprises a three-phase power source.
  • the battery voltage detecting circuit 30 includes two current transformers 30A and a converter 30B.
  • the current transformers 30A are each provided in respective phases of a line for supplying the three-phase a.c. current to the a.c.-d.c. converter circuit 22.
  • Each current transformer 30A detects the current flowing in one phase of the supply line. In other words, a current proportional to the current flowing in the three-phase a.c. supply line is supplied to the converter 30B from each current transformer 30A.
  • the converter 30B converts the value of the applied current to a form suitable for the control by the control circuit 32 and applies the resulting detection signal to the control circuit 32.
  • the control circuit 32 incudes a setting means 32A, a battery voltage controlling amplifier 32B, a battery current controlling amplifier 32C, a gate controller 32D and signal generator 32E. of these component parts, the setting means 32A is provided to preset a desired charged voltage value of the secondary battery 10. A suitable voltage is applied to a terminal 32F and this voltage is divided by a variable resistor thereby presetting the desired charged voltage value. This desired charged voltage value is applied to comparing means 32G. Also applied to the comparing means 32G is the detected value of the battery voltage generated from the battery voltage detecting circuit 28. The detected value and the desired charged voltage value are compared by the comparing means 32G and the difference between the two is applied to the battery voltage controlling amplifier 32B.
  • the battery voltage controlling amplifier 32B applies its output to comparing means 32H. Also applied to the comparing means 32H is the detection signal generated from the converter 30B of the battery current detecting circuit 30.
  • the comparing means 32H compares the inputs and the resulting difference is applied to the battery current controlling amplifier 32C.
  • the battery current controlling amplifier 32C applies its output to the gate controller 32D.
  • the gate controller 32D applies a gate controlling signal or a gate signal to each of the converters 22A and 22B.
  • the generation of the gate signals is controlled in accordance with the output from the signal generator 32E. More specifically, the phase of the gate signal is changed to effect the mode switching between the forward conversion and the inverse conversion operation of the converters 22A and 22B, respectively. In addition, the stopping of the conversion operations, etc., is also effected.
  • This operation corresponds to a case where the operation shown in Fig. 6 is performed.
  • the gate signal generated from the gate controller 32D is controlled in accordance with the command generated from the signal generator 32E thus bringing the converter 22A into the forward conversion operation.
  • the a.c. power is converted to a d.c. power and the secondary battery 10 is charged.
  • This period of operation corresponds to the interval between the times t20 and t21. During this interval, the battery voltage of the secondary battery 10 is compared with the desired charged voltage value by the comparing means 32G.
  • the difference between the battery voltage and the desired charged voltage value is amplified by the battery voltage controlling amplifier 32B and it is then applied to the comparing means 32H.
  • the comparing means 32H compares the applied difference signal with the detection signal from the battery current detecting circuit 30.
  • the difference between the battery voltage and the detection signal from the battery current detecting circuit 30 is amplified by the battery current controlling amplifier 32C and then applied to the gate controller 32D.
  • the applied difference signal controls the phase of a gate signal generated from the gate controller 32D. This control is effected so that the battery voltage of the secondary battery 10 attains the desired charged voltage value.
  • the secondary battery 10 is charged with a constant charging voltage and constant charging current.
  • the signal generator 32E applies an open-circuit command for the converter 22A to the gate controller 32D. This stops the application of the gate signal to the converter 22A by the gate controller 32D. As a result, the operation of the converter 22A is stopped. then, at the time t22, the signal generator 32E applies an inverse conversion command for the converter 22B to the gate controller 32D. Thus, the gate controller 32D applies a gate signal to the converter 22B. When this occurs, the converter 22B starts its inverse conversion operation and the d.c. power from the secondary battery 10 is converted to an a.c. power. The converted a.c. power is sent back to the power source.
  • the signal generator 32E applies an open-circuit command for the converter 22B to the gate controller 32D. This stops the application of the gate signal to the converter 22B by the gate controller 32D. As a result, the operation of the converter 22B is stopped. Then, at the time t24, the signal generator 32E applies a forward conversion operation command for the converter 22B to the gate controller 32D. Thus, the gate controller 32D applies a gate signal to the converter 22B.
  • This gate signal differs in phase from the gate signal generated during the interval from t22 to t23.
  • the control angle is a lead angle and the converter 22B is controlled correspondingly.
  • the control angle is a lag angle thus correspondingly controlling the converter 22B.
  • the signal generator 32E applies an open-circuit command for the converter 22B to the gate controller 32D.
  • the signal generator 32E also applies an operation command for the converter 22A to the gate controller 32D. consequently, the operation of the converter 22B is stopped and at the same time the operation of the converter 22A is started thus starting the reversed discharge of the secondary battery 10.
  • the operation of the converter 22A is stopped in response to the command from the signal generator 32E. Note that the above-mentioned operations are repeated on and after the time t29.
  • Fig. 8 shows another detailed example of the embodiment shown in Fig. 5.
  • the a.c.-d.c. converter circuit 22 comprises a thyristor Ward-Leonard section 220, a step-up circuit 222 and a change-over switch section 224.
  • the thyristor Ward-Leonard section 220 includes converters 220A and 200B arranged in an inverse parallel connection.
  • the converter 220B operates in a different manner from that of the apparatus shown in Fig. 7. More specifically, the converter 220B performs only the inverse conversion operation and no forward conversion operation is performed.
  • the polarity change-over by the changer-over switch section 224 is effected and therefore the forward conversion operation of the converter 220B is not required.
  • a smoothing capacitor 220B is connected across the battery voltage detection circuit.
  • the change-over switch section 224 is controlled by a switching controller 34.
  • the step-up circuit 222 is of the known type disclosed in Japanese Patent No. Publication No. 55-49519. Now beginning with a description of the step-up circuit 222, a thyristor 222B which is in inverse parallel connection with a diode 222A is connected in series between d.c. reactors 220C and 222C. The thyristor 222B is connected with a polarity such that a current flows to the secondary battery 10 from the converters 220A and 220B, respectively. Connected to the cathode of the thyristor 222B is a thyristor 222E which is in inverse parallel connection with a diode 222D. The thyristor 222E is connected such that its anode is connected to the cathode of the thyristor 222B. The step-up circuit 222 is controlled by a step-up controller 36.
  • the construction of the step-up controller 36 is substantially the same as the construction of the control circuit 32 shown in Fig. 7.
  • the step-up controller 36 includes setting means 36A, a voltage controlling amplifier 36B, a current controlling amplifier 36C, a gate controller 36D and a signal generator 36E. A suitable voltage is applied to the setting means 36A from a terminal 36F.
  • the step-up controller 36 also includes comparing means 36G and 36H, a voltage detector 36I and a current detector 36J. The voltage detector 36I and the current detector 36J respectively detect the battery voltage and the battery current of the secondary battery 10.
  • step-up circuit 222 by the step-up controller 36 will now be described briefly. This control is effected by controlling the duration in each of the alternately interchanging ON periods and OFF periods of gate signals which are applied to the thyristors 222B and 222E from the gate controller 36D in accordance with the command of said signal generator 36E.
  • the current flows through the converter 220A, the d.c, reactor 220C, the thyristor 222B, the d.c. reactor 222C and the secondary battery 10 sequentially.
  • the thyristor 222B is turned OFF, and ON gate signal is applied to the thyristor 222E (even in this case, the thyristor 222E remains in OFF state, as will be described later)
  • a high voltage of reverse polarity against the polarity shown in Fig. 8 is generated across both ends of d.c. reactor 222C due to the fact that the current flowing into the d.c. reactor 222C tends to keep flowing in the same direction.
  • This reverse voltage causes the current to flow through a loop formed with the d.c. reactor 222C, the secondary battery 10 and the diode 222D. At this moment, a voltage drop occurs across both ends of said diode 222D. Since this dropped voltage has a reverse polarity in relation to the thyristor 222E, the thyristor 222E remains in OFF state no matter whether ON gate signal is applied thereto.
  • the current flowing through the diode 222D will not vanish rapidly, but will be reduced gradually to zero as time passes, depending on the amount of energy stored in the d.c. reactor 222C, and the terminal voltage of the secondary battery 10. At the zero level, the current will then flow reversely through a loop formed with the secondary battery 10, the d.c. reactor 222C and the thyristor 222E.
  • the thyristors 222B and 222E will repeat their respective ON-OFF operation alternately.
  • the mean value of the current (id) flowing through the d.c. reactor 222C is nil, but if the ON period of the thyristor 222E is longer than that of the thyristor 222B, the mean value of the current (id) becomes a negative value, in which case the current flows from the secondary battery side to the diode 222A side. Accordingly, in the case of the negative mean value of current (id), the electric power is transferred from the secondary battery side to the converter 220B side, whereby the power regeneration is effected to the a.c. power source by means of the converter 220B.
  • Table 2 shows the ON states of the converters 220A and 220B, the diodes 222A and 222D, the thyristors 222B and 222E and the change-over switch section 224 during the respective operating modes shown in Fig. 6.
  • the a.c.-d.c. converter circuit 22 is controlled such that after the normal discharge of the secondary battery 10 has been effected, the reversed charge of the secondary battery 10 is effected.
  • the zinc remaining on each negative electrode of the cell-stack secondary battery 10 after the normal discharge is completely dissolved into the electrolyte by virtue of the reversed charge.
  • the use of the open-circuit condition during the interval from t28 to t29 is arbitrary (optional).
  • electrolyte circulation-type cell-stack secondary battery electrolyte circulating pumps are also stopped as previously during the reversed charge and the reversed discharge.
  • the reversed charge and discharge operations may be performed for every charge and discharge cycle of the secondary battery 10 or at intervals of several cycles.
  • the converter circuit 22 comprised an inverse-parallel connected circuit of a step-up circuit and a thyristor Ward-Leonard section as disclosed in Japanese Patent Publication No. 55-49519. Also, the battery current detecting circuit 30 detected the currents corresponding to the charging and discharging d.c. current values in the form of alternating currents.
  • the energy stored in the secondary battery is regenerated or returned to the a.c. power source even in the reversed charge and discharge modes and effective utilization of the energy is ensured.
  • the secondary battery operating method of this invention has the effect of satisfactorily preventing the occurence of abnormal electrodeposition of zinc and increasing the charge and discharge cycle life of secondary batteries.

Claims (6)

  1. Verfahren zum Betreiben einer Sekundärbatterie (10), um die Batterie wieder instandzusetzen, wobei die Sekundärbatterie zumindest eine Einheitszelle aufweist, die als aktives Material für die negative Elektrode (10M) in einem Elektrolyten Zink verwendet und so aufgebaut ist, um sie wiederholt laden und entladen zu können, wobei das Verfahren folgende Schritte enthält:
    Entladen der Sekundärbatterie, bis die Batteriespannung auf einen vorgegebenen positiven Wert herabgesetzt wurde; und dann
    elektrisches und umschaltbares Verbinden der positiven Elektrode (10P) der Batterie mit dem negativen Ausgang (20M) einer Gleichstromquelle (20) sowie Verbinden der negativen Elektrode der Batterie mit dem positiven Ausgang (20P) der Gleichstromquelle; und
    Fließen eines umgekehrten Ladestroms von der negativen Elektrode zur positiven Elektrode durch den Elektrolyten der Batterie von der Gleichstromquelle, bis die Batteriespannung weiter unterhalb des Nullwerts herabgesetzt wurde und einen vorgegebenen negativen Wert erreicht hat, damit das Zink auf der negativen Elektrode im Elektrolyten vollständig gelöst wird; elektrisches und umschaltbares Verbinden der positiven Elektrode (10P) der Batterie mit dem positiven Ausgang (20P) der Gleichstromquelle (20) und der negativen Elektrode (10M) der Batterie mit dem negativen Ausgang (20M) der Gleichstromquelle (20); und
    Fließen eines umgekehrten Entladestroms von der positiven Elektrode zur negativen Elektrode durch den Elektrolyten der Batterie von der Gleichstromquelle (20), bis die Batteriespannung über den Nullwert angestiegen ist und eine Batterieladespannung erreicht hat;
    wobei die umgekehrten Lade- und Entladevorgänge für jeden normalen Lade- und Entladezyklus der Sekundärbatterie (10) oder in Intervallen von mehreren Zyklen durchgeführt werden.
  2. Verfahren gemäß Anspruch 1, wobei das Verfahren weiters das Einleiten eines Ladevorgangs der Sekundärbatterie (10) enthält, nachdem die Batteriespannung auf die Batterieladespannung erhöht wurde.
  3. Verfahren gemäß Anspruch 1 oder 2, wobei der Umlauf des Elektrolyten in der Batterie während jener Zeit angehalten wird, in der die Batteriespannung vom vorgegebenen positiven Wert auf den vorgegebenen negativen Wert herabgesetzt wird.
  4. Verfahren gemäß Anspruch 1 oder 2, wobei der Umlauf des Elektrolyten in der Batterie während jener Zeit angehalten wird, in der die Batteriespannung vom vorgegebenen negativen Wert auf die Batterieladespannung erhöht wird.
  5. Verfahren gemäß jedem der bisherigen Ansprüche, wobei die Gleichstrom-(dc)-Leistung zur Gleichstromversorgung (20) von einer Wechselstrom-(ac)-Quelle (26) über eine Wechselspannungs/Gleichspannungs-Umsetzerstufe (22) geliefert wird, und wobei während jener Zeit, in der die Batteriespannung von dem vorgegebenen positiven Wert auf den Nullwert herabgesetzt wird, das Verfahren weiters folgende Schritte enthält:
    Umsetzen der Gleichspannung der Batterie in eine Stufen-Wechselspannung mit Hilfe einer Stufenschaltung der Wechselspannungs/Gleichspannungs-Umsetzerstufe; und
    Rückführen der Stufen-Wechselspannung zur Wechselspannungsquelle.
  6. Verfahren gemäß jedem der Ansprüche 1 bis 4, wobei die Gleichspannungleistung der Gleichspannungsquelle (20) von einer Wechsel-(ac)-Spannungsquelle über eine Wechselspannungs/Gleichspannungs-Umsetzerstufe geliefert wird, und wobei zwischen der Änderung vom negativen Wert auf Null während jener Zeit, in der die Batteriespannung auf die Batterieladespannung vom vorgegebenen negativen Wert angehoben wird, das Verfahren folgende Schritte enthält:
    Umsetzen der Gleichspannungsleistung der Batterie in eine Stufen-Wechselspannung mit Hilfe einer Stufenschaltung der Wechselspannungs/Gleichspannungs-Umsetzerstufe; und
    Rückführen der Stufen-Wechselspannung zur Wechselspannungsquelle.
EP85303944A 1983-12-07 1985-06-04 Verfahren zum Betrieb einer Sekundärbatterie Expired - Lifetime EP0204038B1 (de)

Priority Applications (2)

Application Number Priority Date Filing Date Title
DE8585303944T DE3583863D1 (de) 1985-06-04 1985-06-04 Verfahren zum betrieb einer sekundaerbatterie.
AT85303944T ATE66546T1 (de) 1985-06-04 1985-06-04 Verfahren zum betrieb einer sekundaerbatterie.

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP58229876A JPS60124372A (ja) 1983-12-07 1983-12-07 二次電池の運転方法

Publications (2)

Publication Number Publication Date
EP0204038A1 EP0204038A1 (de) 1986-12-10
EP0204038B1 true EP0204038B1 (de) 1991-08-21

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US (1) US4691158A (de)
EP (1) EP0204038B1 (de)
JP (1) JPS60124372A (de)

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JPH0419673B2 (de) 1992-03-31
US4691158A (en) 1987-09-01
EP0204038A1 (de) 1986-12-10
JPS60124372A (ja) 1985-07-03

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